EP1737934B1 - Method and device for processing a butadiene-containing feedstock - Google Patents

Method and device for processing a butadiene-containing feedstock Download PDF

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Publication number
EP1737934B1
EP1737934B1 EP05742728A EP05742728A EP1737934B1 EP 1737934 B1 EP1737934 B1 EP 1737934B1 EP 05742728 A EP05742728 A EP 05742728A EP 05742728 A EP05742728 A EP 05742728A EP 1737934 B1 EP1737934 B1 EP 1737934B1
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EP
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Prior art keywords
column
feed
fraction
acetylenic compounds
fractionation zone
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EP05742728A
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German (de)
French (fr)
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EP1737934A1 (en
Inventor
Sylvain Louret
Vincent Coupard
Reynald Bonneau
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/141—Fractional distillation or use of a fractionation or rectification column where at least one distillation column contains at least one dividing wall
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects

Definitions

  • the invention relates to the field of processes and installations for the treatment of a feed comprising butadiene, C5 + unsaturates, and acetylenic compounds, especially for the elimination of acetylenics and the fractionation of the feedstock to produce butadiene.
  • Cn + refers to hydrocarbons with n or more carbon atoms, but can also refer to hydrocarbons with n carbon atoms exclusively (Cn).
  • the improvement provided by the present invention relates mainly to the implementation of a distillation comprising a step of pre-fractionation of the feed, and a complementary fractionation step in a zone separated from the feed zone of the feed. pre-fractionation, allowing the withdrawal of a current to hydrogenate rid of a significant portion of the pollutants of hydrogenation catalysts.
  • the improvement also relates to the fact that the hydrogenation step relates to a fraction rich in acetylenic compounds and poor in C5 +
  • the invention relates to a process for the treatment of a filler comprising acetylenic compounds, butadiene, and a C5 + fraction comprising diethylenic and / or acetylenic compounds, for example pentadiene and / or cyclopentadiene, in which the charge is a distillation step, recovering a C4 cut comprising substantially all the butadiene, recovering a C5 + enriched cut, and producing a fraction containing acetylenic compounds, treating at least a portion of the fraction enriched acetylenic compounds in a at least one hydrogenation step, and a depleted effluent of acetylenic compounds from the hydrogenation step is recycled to the distillation step.
  • One of the objects of the process of the invention is to selectively hydrogenate the acetylenic compounds contained in the feedstock in the presence of hydrogen while minimizing the deactivation of the hydrogenation catalyst by oligomers, polymers, and their precursors.
  • Another object of the process of the invention is to purify in a thorough manner (in particular extensive elimination of acetylenics) a charge which can be very rich in butadiene, without substantially reducing the cycle time of the hydrogenation catalyst, while minimizing the maximum butadiene losses.
  • the invention is described below with references which relates to the figure 1 .
  • part A is "distinct and non-adjacent" to part B, if A and B are disjoint and therefore have no common part, and if a plate of A is separated from a B plateau which is above or below it by at least 1 theoretical plateau.
  • This also applies to trays of A and B located at the same level but on both sides of a vertical partition in the column.
  • the trays being separated by said partition and not being one above the other, they can therefore be considered “non-adjacent".
  • the "lower trays” are the trays on which the plateau liquid supply (receiving the liquid part of the charge) flows, in cascade. These lower trays therefore do not include trays located at a level lower than that of the load supply, but in an isolated area of this power supply.
  • the invention therefore makes it possible to operate a fractionation in two stages, in which the second stage is at least partly carried out in a zone that is quite distinct and not adjacent to the feed zone of the load. This separation, or this distance, avoids the dilution of the products circulating in this zone by the impurities present in the feed. It is indeed common that the feedstock contains undesirable products for the isomerization catalyst: traces of oligomers and polymers, relatively heavy diethylenic compounds and / or acetylenic C5 + likely to form additional heavier products (oligomers and polymers) or even small amounts of solid coke particles.
  • the withdrawal from A at a point such that the C4 / C5 + molar ratio is greater than that of the feed makes it possible to limit the presence of undesirable C5 + compounds precursors of oligomers and polymers. This therefore makes it possible to send to the hydrogenation a product comprising a reduced amount of pollutants capable of degrading the efficiency and of the hydrogenation catalyst.
  • the hydrogenation catalysts are typically inhibited by significant amounts of oligomers or polymers, or their precursors including diethylenic and acetylenic heavier.
  • the catalyst less polluted, is more efficient, typically more selective (for the hydrogenation of acetylenic preserving at best butadiene, including because it can operate under substantially optimal operating conditions without having to compensate for the deactivation by modifying the operating conditions), and has an increased lifetime. It also allows for further purification, with lower losses of butadiene.
  • the withdrawn fraction is drawn off at a column level higher than the feed point of the feedstock. This contributes to greatly increase the C4 / C5 + ratio of the fraction taken.
  • the recycling of the effluent depleted of acetylenic compounds from the hydrogenation step is carried out at a level of the distillation column located above the withdrawal level of the fraction taken, and above the parts A and B
  • “above” is meant according to the invention that the recycling is not only carried out at a higher level, but also that it causes an internal liquid reflux in the two zones A and B (typically in parallel or in parallel). series).
  • this recycling causes an absorption of acetylenic, which is refluxed down the column, to obtain a concentration effect of these acetylenic in the fraction taken.
  • the cut comprising butadiene at the top of the column contains only very few acetylenics.
  • the withdrawal point of this fraction taken can advantageously be located at the point of maximum concentration of acetylenic, in particular vinyl acetylene, or near this point.
  • the part A is constituted by a section of said column located above the supply of the load (typically several theoretical plates above).
  • the column comprises 45 theoretical plates, and the feed is fed to the plate 25, a fraction taken off the tray 20 can be withdrawn and recycled after hydrogenation to the plate 10.
  • Part B is then constituted by plates 25 to 45. It is then possible to define a portion A distinct and not adjacent to B, which is constituted (for example) by plates 14 to 21.
  • the complementary fractionation zone is typically formed in this case by the trays 1 to 21, and the pre-fractionation zone by the trays 22 to 45.
  • the distillation column comprises a partition arranged so as to separate the part A of the complementary fractionation zone, from zone B, and in that the pre-fractionation zone (4a, 4b , 6, 7) and the complementary fractionation zone (5, 6, 7) comprise at least one common section (6, 7).
  • the hydrogenation step is carried out in the presence of hydrogen, in a catalyst bed, for example based on palladium / gold, or palladium / silver, or any other known selective hydrogenation catalyst.
  • a catalyst bed for example based on palladium / gold, or palladium / silver, or any other known selective hydrogenation catalyst.
  • the choice of catalyst is not an essential element of the invention.
  • the intermediate stream is directly sent to a catalyst bed in the presence of hydrogen located in said part A of the complementary fractionation zone, below the theoretical top plate of said part A, for example in the half
  • the effluent depleted of acetylenic compounds is recycled in the common section at the top of the column, preferably several theoretical plates (3 to 15 for example) above the zones A and B, in order to achieve a good reflux of the acetylenic compounds. This makes it possible to obtain a thorough elimination of acetylenics.
  • Such a device preferably used with an implementation according to one or more of the aforementioned process arrangements (for example recycling of the hydrogenation effluent above (and preferably from 3 to 15 theoretical trays above the zones). A and B)) makes it possible to obtain the advantages described for the process according to the invention.
  • the column may comprise, in some or all zones, packing, structured or not, instead of trays, which constitutes a technical equivalent of these trays.
  • this partition may consist essentially of a wall, or internal partition.
  • This inner wall may extend along an axis parallel to the longitudinal axis of the distillation column.
  • This inner wall may be substantially vertical or inclined at an angle to the vertical less than 45 °.
  • the partition may also consist of internal walls arranged between each plate on a section of the column.
  • the distillation column may typically comprise a total number of trays (unless otherwise stated, theoretical plates, counted from the top of the column) of between 20 and 50, preferably between 35 and 45.
  • the pre-fractionation zone and the complementary fractionation zone may typically comprise the same number or a different number of theoretical plates.
  • the pre-fractionation zone or the complementary fractionation zone may generally comprise between 4 and 15, preferably between 9 and 12 theoretical plates which are separated and not in common.
  • the common section at the head of the column can comprise between 1/3 and 2/3 of the total number of theoretical plates.
  • it may comprise from 10 to 30, preferably from 12 to 25 theoretical plates.
  • the common section at the bottom of the column may, for its part, generally comprise from 2 to 10 theoretical plates.
  • the feedstock may be a fraction of a steam cracking effluent comprising, for the most part, hydrocarbons having between 4 and 5 carbon atoms, preferably predominantly 4 carbon atoms.
  • the filler may comprise at least 50% by weight, preferably 70% by weight, more preferably 90% by weight of hydrocarbons having between 4 and 5 carbon atoms, or even 4 carbon atoms.
  • the withdrawal rate of the collected fraction comprising acetylenics may advantageously be maintained at a value substantially equal to that of the feed rate of the feedstock.
  • the withdrawal rate of this fraction taken can be maintained between 70% and 130% of the value of the flow rate of the charge, preferably between 90% and 110% of the value of the flow rate of the charge.
  • the feedstock is fed from a line (1) into a distillation column (2) having a pre-fractionation zone (6, 4a, 4b, 7), a complementary fractionation zone (6, 5, 7), and a partition (3) arranged in the central part so as to separate a part (4a, 4b) of the pre-fractionation zone on the feed side of the load from a part A (5) of the fractionation zone complementary.
  • the partition (3) is arranged in the column (2) so as to provide a common section (6) at the top of the column and a common section (7) at the bottom of the column, between the two fractionation zones mentioned above.
  • a reduced C5 + content intermediate stream (relative to the feedstock), vaporizes out of the upper tray of zone 4a, and feeds the complementary fractionation zone (6, 5, 7) at the lower plateau of the zone. commune (6).
  • the liquid of this plate is distributed between the zones (4a) and (5).
  • the steam flow from the upper plateau of the common zone (7) is distributed equally between zones (4b) and (5).
  • a fraction rich in acetylenic compounds, produced in part A (5) of the complementary fractionation zone, is withdrawn by a lateral withdrawal line (11) before being sent to a bed of hydrogenation catalyst (12) to inside a hydrogenation reactor (13).
  • the catalyst bed is a fixed bed with downward flow, that is to say that the fraction taken is introduced from above into the hydrogenation reactor.
  • Hydrogen is injected into the hydrogenation reactor via a line (14).
  • An effluent depleted of acetylenic compounds is recovered by a pipe (15). This depleted effluent of acetylenic compounds is cooled in a heat exchanger (16) before being recycled. in the common section 6 at the top of the distillation column (2), via a pipe (17).
  • a cut C4 comprising substantially all the butadiene is also recovered via a pipe (21). This section is then sent via line (21) into a condenser (22) and into a separator (24) via a pipe (23). Part of this cut C4 is sent in the column (2), in the form of reflux, through a pipe (25). The other part of the C4 cut is recovered by the pipe (26).
  • a cut C5 enriched in oligomers is recovered via a line 31.
  • Part of this cut C5 is sent through a pipe (32) in a reboiler (33) before being recycled to the bottom of the column by a pipe (34).
  • the other part of the C5 cut is recovered by a pipe (35).
  • the fraction comprising acetylenic compounds produced in the upper portion of the portion A (5) of the complementary fractionation zone is directly sent into a bed of hydrogenation catalyst (51), this bed being located in the internal portion A to the column, and not inside a separate hydrogenation reactor.
  • the catalyst bed is a fixed downflow bed, ie the fraction enriched in acetylenic compounds is introduced through the top of the catalyst bed (51).
  • Hydrogen is injected from below into the hydrogenation catalyst bed (51) via a line (52).
  • a liquid effluent depleted of compounds acetylenic acid is recovered below the catalyst bed (51), and a part of this effluent is recycled (using a pump not shown) by the line (56) above the zones (4a, 4b and 5) (for example 4 or 5 theoretical plates above), to increase acetylenic poor internal reflux, in the A (5) and B (4b, 7) portions of the column.
  • a C4 + C5 feedstock from steam cracking effluents is treated according to the process of the prior art (EP1217060A1 ).
  • the feed is introduced into a distillation column at a temperature of 64 ° C., a pressure of 0.60 MPa and a flow rate of 30 T / h.
  • This column has about 40 theoretical plates (between 50 and 120 real trays according to the type of trays) and the load is introduced at the 20 th plateau (theoretical).
  • the column is maintained at a pressure of 0.50 MPa at the top and 0.53 MPa at the bottom.
  • the temperature in the column is maintained at 45 ° C overhead and 95 ° C bottom.
  • a C4 cut containing butadiene and approximately 1200 ppm of acetylenic compounds is recovered.
  • the composition of this C4 cut is presented in Table 1 below. Part of this cut is reintroduced after condensation and separation, in the form of reflux, at the top of the column, while the other part is recovered for further processing, by example a solvent extraction.
  • the reflux ratio that is to say the ratio between the portion of the C4 cut reintroduced at the top of the column and the totality of the C4 cut recovered at the top of the column, is 2.2.
  • the ratio of acetylenic compounds Merger butadiene is substantially the highest of the column, the occurrence equal to 0.025 mol / mol.
  • the withdrawal rate of this fraction taken is equal to the feed rate of the load.
  • An effluent depleted in acetylenic compounds is collected and then cooled before being recycled to the column at the level of the 6 th theoretical plateau.
  • the cooling is carried out in such a way that the temperature of this effluent is approximately the same as that of the theoretical 6 th plateau.
  • This effluent depleted in acetylenic compounds contains in particular the olefinic compounds initially present in the feedstock, the butadienes which have not been hydrogenated as well as the oligomers produced in the hydrogenation zone. These oligomeric compounds, which are heavy products, are collected in the bottom of column. A C5 cut comprising these compounds is taken from the bottom of the column, the composition of which is shown in Table 1 below. Part of this C5 cut is introduced into a reboiler and recycled at the bottom of the column.
  • the feed level of the feed in the column (20 th plateau), the level of side withdrawal of the fraction taken (23 th plateau) and the recycling level of the hydrogenated effluent (6 th plateau) were chosen in order to obtain 1200 ppm by weight of acetylenic in the C4 cut while minimizing the loss of 1,3-butadiene.
  • VAC vinyl acetylenic compounds
  • Losses of butadiene represent the amount of butadiene which is not recovered at the top of the column, ie butadiene which is hydrogenated to butene at the hydrogenation reactor to which is added butadiene which is lost in the bottom column in section C5.
  • the losses of 1,3-butadiene, the commercially interesting isomer, are 2.85% by weight.
  • the C5 content at the top of the column is 1.00% by weight.
  • a steam cracking charge C4 + C5 having a composition identical to that of Example 1 is sent into the device of the Figure 1 .
  • This feed is introduced into a distillation column having an inner wall, under the same conditions of pressure and temperature as in Example 1.
  • Example 2 At the top of the column is recovered a C4 cut containing butadiene.
  • the composition of this C4 cut is presented in Table 2 below.
  • part of this cup is reintroduced after condensation and separation, in the form of reflux, at the top of the column, while the other part is recovered for further processing.
  • the reflux ratio relative to the distillate is 1.7.
  • This collected fraction rich in acetylenic compounds is introduced into a hydrogenation reactor fed with hydrogen under the same conditions as in Example 1.
  • a depleted effluent acetylenic compounds is recovered and then cooled before being recycled to the column at the 6 th theoretical plate of the common section (6) in the column heading.
  • the cooling is carried out in such a way that the temperature of this effluent is approximately the same as that of this theoretical 6 th plateau.
  • a C5 cut is taken from the bottom of the column. Part of this C5 cut is introduced into a reboiler and recycled at the bottom of the column.
  • the feed level of the feedstock in the column (20 th theoretical plateau), the level of lateral withdrawal of the fraction taken (16 th theoretical plateau) and the level of recycling of the hydrogenated effluent (6 th theoretical plateau) were chosen in order to obtain a loss of 1,3-butadiene of 2.85% by weight, which corresponds to the loss obtained in Example 1.
  • VAC vinyl acetylenic compounds
  • the content of acetylenic compounds at the top of the column is 1100 ppm for a loss of 1,3 butadiene identical to Example 1.
  • the C5 content at the top of the column is 0.33% by weight.
  • the ratio C4 / C5 + (C4 / C5) of the effluent removed is more than 30% higher than that of Example 1, indicating a significantly lower amount of pentadiene, and cyclopentadiene which are precursors of oligomers and polymers.
  • the amounts of oligomers and polymers and traces of C6 + possibly present in the charges are also greatly reduced.
  • the service life, as well as the selectivity of the hydrogenation catalyst are thus significantly increased.
  • Example 2 The installation of Example 2 is repeated, but instead of aiming at a loss of 1,3-butadiene identical to that of Example 1, the aim is a content of acetylenic compounds at the head of the column identical to that obtained in this same Example 1, ie 1200 ppm.
  • a steam cracking charge C4 + C5 having a composition identical to that of Example 1 is sent into the device of the Figure 1 .
  • This feed is introduced into a distillation column having an inner wall under the same conditions of pressure and temperature as in Example 2.
  • Example 2 the charge is introduced at the 20 th theoretical plate, the column itself having 40 theoretical plates.
  • the column is maintained under the same pressure and temperature conditions as in Example 2.
  • the ratio of acetylenic compounds concentrations of butadiene is equal to 0.03 mol / mol.
  • the withdrawal rate of this fraction is 30 T / h.
  • This fraction enriched in acetylenic compounds is introduced into a hydrogenation reactor fed with hydrogen under the same conditions as in Examples 1 and 2.
  • a depleted effluent acetylenic compounds is recovered and then cooled before being recycled to the column at the 6 th theoretical plate from the common section at the column head. As in Examples 1 and 2, the cooling is carried out in such a way that the temperature of this effluent is approximately the same as that of this theoretical 6 th plateau.
  • a C5 cut is taken at the bottom of the column, the composition of which is shown in Table 3 below. Part of this C5 cut is introduced into a reboiler and recycled at the bottom of the column.
  • Losses of 1,3-butadiene are 2.75%.
  • the C5 content at the top of the column is 0.38% by weight.
  • the C4 / C5 ratio is increased in a proportion substantially identical to that of Example 2.

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Abstract

The invention concerns a process and apparatus for treating a feed comprising ethylenic and acetylenic compounds. In the process of the invention, the feed is sent to a distillation step, a C4 cut and a C5+ cut are recovered, a drawn fraction comprising acetylenic compounds is treated in at least one hydrogenation step, and an effluent which is depleted in acetylenic compounds is recycled. The distillation step comprises: an initial step for pre-fractionating the feed, carried out in a pre-fractionation zone included in a distillation column; and at least one complementary fractionation step, carried out in a zone which comprises a portion A, which is distinct from and not adjacent to the portion B of the pre-fractionation zone below the supply, in which the fraction drawn from a point in A is recovered with a C4/C5+ ratio that is higher than that of the feed.

Description

Domaine de l'inventionField of the invention

L'invention concerne le domaine des procédés et des installations pour le traitement d'une charge comportant du butadiène , des insaturés en C5+, et des composés acétyléniques, pour notamment l'élimination des acétyléniques et le fractionnement de la charge pour produire du butadiène. Le terme Cn+ se rapporte à des hydrocarbures à n atomes de carbone ou plus, mais peut aussi se rapporter à des hydrocarbures à n atomes de carbone exclusivement (Cn).The invention relates to the field of processes and installations for the treatment of a feed comprising butadiene, C5 + unsaturates, and acetylenic compounds, especially for the elimination of acetylenics and the fractionation of the feedstock to produce butadiene. The term Cn + refers to hydrocarbons with n or more carbon atoms, but can also refer to hydrocarbons with n carbon atoms exclusively (Cn).

Art antérieurPrior art

Il est connu de la demande de brevet européenne EP 1 217 060 d'envoyer une charge dans une étape de distillation dans laquelle on récupère une coupe C4 comportant sensiblement tout le butadiène, une coupe C5+, et une fraction riche en composés acétyléniques par soutirage latéral, de traiter la fraction riche en composés acétyléniques dans une étape d'hydrogénation, et de recycler un effluent appauvri en composés acétyléniques issu de l'étape d'hydrogénation dans l'étape de distillation.It is known from the European patent application EP 1 217 060 to feed a feedstock into a distillation step in which a C4 cut comprising substantially all the butadiene, a C5 + cut, and a fraction rich in acetylenic compounds is recovered by lateral withdrawal, to treat the fraction rich in acetylenic compounds in a step of hydrogenation, and recycle a depleted effluent of acetylenic compounds from the hydrogenation step in the distillation step.

Il existe un besoin de parvenir à hydrogéner, avec une sélectivité améliorée, les composés acétyléniques contenus dans ce type de charge, et ceci dans des conditions ou le catalyseur d'hydrogénation ne se désactive que très lentement.There is a need to be able to hydrogenate, with improved selectivity, the acetylenic compounds contained in this type of filler, and this under conditions where the hydrogenation catalyst deactivates only very slowly.

Il existe également un besoin de limiter les pertes en butadiène liées à la distillation et l'hydrogénation d'une charge très riche en butadiène.There is also a need to limit butadiene losses associated with the distillation and hydrogenation of a very rich butadiene feedstock.

Description sommaire de l'inventionBrief description of the invention

L'amélioration apportée par la présente invention porte principalement sur la mise en oeuvre d'une distillation comportant une étape de pré-fractionnement de la charge, et d'une étape de fractionnement complémentaire dans une zone séparée de la zone de l'alimentation du pré-fractionnement, permettant le soutirage d'un courant à hydrogéner débarrassé d'une partie notable des polluants des catalyseurs d'hydrogénation.The improvement provided by the present invention relates mainly to the implementation of a distillation comprising a step of pre-fractionation of the feed, and a complementary fractionation step in a zone separated from the feed zone of the feed. pre-fractionation, allowing the withdrawal of a current to hydrogenate rid of a significant portion of the pollutants of hydrogenation catalysts.

L'amélioration porte également sur le fait que l'étape d'hydrogénation porte sur une fraction riche en composés acétyléniques et pauvre en C5+The improvement also relates to the fact that the hydrogenation step relates to a fraction rich in acetylenic compounds and poor in C5 +

Description détaillée de l'inventionDetailed description of the invention

L'invention concerne un procédé de traitement d'une charge comprenant des composés acétyléniques, du butadiène, et une fraction C5+ comprenant des composés diéthyléniques et/ou acétyléniques, par exemple du pentadiène et/ou du cyclopentadiène, dans lequel on envoie la charge dans une étape de distillation, on récupère une coupe C4 comportant sensiblement tout le butadiène, on récupère une coupe enrichie en C5+, et on produit une fraction prélevée comprenant des composés acétyléniques, on traite au moins une partie de la fraction enrichie en composés acétyléniques dans au moins une étape d'hydrogénation, et on recycle un effluent appauvri en composés acétyléniques issu de l'étape d'hydrogénation dans l'étape de distillation.The invention relates to a process for the treatment of a filler comprising acetylenic compounds, butadiene, and a C5 + fraction comprising diethylenic and / or acetylenic compounds, for example pentadiene and / or cyclopentadiene, in which the charge is a distillation step, recovering a C4 cut comprising substantially all the butadiene, recovering a C5 + enriched cut, and producing a fraction containing acetylenic compounds, treating at least a portion of the fraction enriched acetylenic compounds in a at least one hydrogenation step, and a depleted effluent of acetylenic compounds from the hydrogenation step is recycled to the distillation step.

Un des objets du procédé de l'invention est d'hydrogéner sélectivement les composés acétyléniques contenus dans la charge en présence d'hydrogène en minimisant la désactivation du catalyseur d'hydrogénation par des oligomères, polymères, et leurs précurseurs.One of the objects of the process of the invention is to selectively hydrogenate the acetylenic compounds contained in the feedstock in the presence of hydrogen while minimizing the deactivation of the hydrogenation catalyst by oligomers, polymers, and their precursors.

Un autre objet du procédé de l'invention est de purifier de façon poussée (notamment élimination poussée d'acétyléniques) une charge qui peut être très riche en butadiène, sans réduire sensiblement la durée de cycle du catalyseur d'hydrogénation, tout en minimisant au maximum les pertes en butadiène. L'invention est décrite ci-après avec des références qui se rapporte à la figure 1.Another object of the process of the invention is to purify in a thorough manner (in particular extensive elimination of acetylenics) a charge which can be very rich in butadiene, without substantially reducing the cycle time of the hydrogenation catalyst, while minimizing the maximum butadiene losses. The invention is described below with references which relates to the figure 1 .

Il a été trouvé un procédé de traitement d'une charge comprenant des composés acétyléniques, du butadiène, et une fraction C5+ comprenant des composés diéthyléniques et/ou acétyléniques, par exemple du pentadiène et/ou du cyclopentadiène, dans lequel :

  1. i) on envoie la charge dans une étape de distillation, on récupère une coupe C4 comportant sensiblement tout le butadiène, on récupère une coupe enrichie en C5+ et on produit une fraction prélevée comprenant des composés acétyléniques,
  2. ii) on traite au moins une partie de ladite fraction prélevée dans au moins une étape d'hydrogénation, et
  3. iii) on recycle un effluent appauvri en composés acétyléniques issu de l'étape d'hydrogénation dans l'étape de distillation,
    caractérisé en ce que l'étape de distillation comporte :
    • une étape initiale de pré-fractionnement de la charge, qui est alimentée dans une zone de pré-fractionnement (4a, 4b, 6, 7) comprise dans une colonne de distillation, pour obtenir à un ou plusieurs niveaux intermédiaires de la colonne au moins un courant intermédiaire à teneur réduite en C5+, et
    • au moins une étape de fractionnement par distillation de ce ou ces courant(s) intermédiaire(s), mise en oeuvre dans une zone de fractionnement complémentaire dont une partie A (5) au moins est distincte et non adjacente à la partie B (4b, 7) de la zone de pré-fractionnement constituée par le plateau l'alimentation de la charge et les plateaux inférieurs, pour soutirer la fraction prélevée à partir d'un point de A pour lequel le rapport molaire [C4 / C5+] est plus élevé que celui de la charge.
A method of treating a feed comprising acetylenic compounds, butadiene, and a C5 + fraction comprising compounds has been found. diethylenic and / or acetylenic, for example pentadiene and / or cyclopentadiene, in which:
  1. i) the feedstock is sent to a distillation step, a C4 cut comprising substantially all the butadiene is recovered, a C5 + enriched cut is recovered and a cut fraction comprising acetylenic compounds is produced,
  2. ii) treating at least a portion of said fraction taken in at least one hydrogenation step, and
  3. iii) recycling an effluent depleted of acetylenic compounds from the hydrogenation step in the distillation step,
    characterized in that the distillation step comprises:
    • an initial step of pre-fractionation of the feed, which is fed into a pre-fractionation zone (4a, 4b, 6, 7) included in a distillation column, to obtain at one or more intermediate levels of the column at least an intermediate stream with reduced C5 + content, and
    • at least one step of fractionation by distillation of this or these intermediate stream (s), implemented in a complementary fractionation zone of which at least one part A (5) is distinct and not adjacent to part B (4b) , 7) of the pre-fractionation zone constituted by the feed tray and the lower trays, to withdraw the fraction taken from a point of A for which the molar ratio [C4 / C5 +] is more high than that of the charge.

Selon l'invention, on considère que la partie A est "distincte et non adjacente" à la partie B, si A et B sont disjointes et n'ont donc pas de partie commune, et si un plateau de A est séparé d'un plateau de B qui est au dessus ou en dessous de lui par au moins 1 plateau théorique. Ceci s'applique aussi à des plateaux de A et B situés au même niveau mais de part et d'autre d'une cloison verticale dans la colonne. Les plateaux étant séparés par ladite cloison et n'étant pas l'un au dessus de l'autre, ils peuvent donc être considérés "non adjacents". Il n'y a pas nécessairement de séparation matérielle telle qu'une cloison entre A et B. Les "plateaux inférieurs" sont les plateaux sur lesquels le liquide du plateau d'alimentation (recevant la partie liquide de la charge) s'écoule, en cascade. Ces plateaux inférieurs ne comprennent donc pas des plateaux situés à un niveau inférieur à celui de l'alimentation de la charge, mais dans une zone isolée de cette alimentation.According to the invention, it is considered that part A is "distinct and non-adjacent" to part B, if A and B are disjoint and therefore have no common part, and if a plate of A is separated from a B plateau which is above or below it by at least 1 theoretical plateau. This also applies to trays of A and B located at the same level but on both sides of a vertical partition in the column. The trays being separated by said partition and not being one above the other, they can therefore be considered "non-adjacent". There is not necessarily any physical separation such as a partition between A and B. The "lower trays" are the trays on which the plateau liquid supply (receiving the liquid part of the charge) flows, in cascade. These lower trays therefore do not include trays located at a level lower than that of the load supply, but in an isolated area of this power supply.

L'invention permet donc d'opérer un fractionnement en deux étapes, dans lequel la deuxième étape est au moins en partie réalisée dans une zone bien distincte et non adjacente à la zone d'alimentation de la charge. Cette séparation, ou cet éloignement, évite la dilution des produits circulant dans cette zone par les impuretés présentes dans l'alimentation. Il est en effet fréquent que la charge contienne des produits indésirables pour le catalyseur d'isomérisation: traces d'oligomères et de polymères, composés relativement lourds diéthyléniques et/ou acétyléniques en C5+ susceptibles de former des produits plus lourds additionnels (oligomères et polymères), voire même de petites quantités de particules solides de coke.The invention therefore makes it possible to operate a fractionation in two stages, in which the second stage is at least partly carried out in a zone that is quite distinct and not adjacent to the feed zone of the load. This separation, or this distance, avoids the dilution of the products circulating in this zone by the impurities present in the feed. It is indeed common that the feedstock contains undesirable products for the isomerization catalyst: traces of oligomers and polymers, relatively heavy diethylenic compounds and / or acetylenic C5 + likely to form additional heavier products (oligomers and polymers) or even small amounts of solid coke particles.

Selon l'invention, tous ces composés indésirables relativement lourds vont avoir tendance à refluer vers le bas de la zone de pré-fractionnement, et donc à descendre dans la partie B de cette zone (partie comprenant le plateau d'alimentation et les plateaux en dessous (en communication de liquide avec ces plateaux)), pour finalement sortir en fond de colonne. La mise en oeuvre d'une zone de fractionnement complémentaire dont une partie A est distincte et non adjacente à B permet de soustraire A, au moins en partie, à l'influence des composés indésirables précités, notamment oligomères et polymères qui descendent en majorité dans la zone B.According to the invention, all these relatively heavy undesirable compounds will tend to flow down the pre-fractionation zone, and thus to go down in the part B of this zone (part comprising the feed tray and the trays in below (in liquid communication with these trays)), finally to go out at the bottom of the column. The implementation of a complementary fractionation zone of which part A is distinct and non-adjacent to B makes it possible to subtract A, at least in part, from the influence of the abovementioned undesirable compounds, in particular oligomers and polymers, which predominantly fall within zone B.

Le soutirage, à partir de A, en un point tel que le rapport molaire C4/C5+ est supérieur à celui de la charge permet de limiter la présence de composés indésirables en C5+ précurseurs d'oligomères et polymères. Cela permet donc d'envoyer à l'hydrogénation un produit comprenant une quantité réduite de polluants susceptibles de dégrader l'efficacité et du catalyseur d'hydrogénation. Les catalyseurs d'hydrogénation sont en effet typiquement inhibés par des quantités notables d'oligomères ou de polymères, ou de leurs précurseurs notamment diéthyléniques et acétyléniques les plus lourds.The withdrawal from A at a point such that the C4 / C5 + molar ratio is greater than that of the feed makes it possible to limit the presence of undesirable C5 + compounds precursors of oligomers and polymers. This therefore makes it possible to send to the hydrogenation a product comprising a reduced amount of pollutants capable of degrading the efficiency and of the hydrogenation catalyst. The hydrogenation catalysts are typically inhibited by significant amounts of oligomers or polymers, or their precursors including diethylenic and acetylenic heavier.

Le catalyseur, moins pollué, est plus efficace, typiquement plus sélectif (pour l'hydrogénation des acétyléniques en préservant au mieux le butadiène, notamment du fait qu'il peut fonctionner dans les conditions opératoires sensiblement optimales sans devoir compenser la désactivation par modification des conditions opératoires), et a une durée de vie accrue. Il permet aussi d'obtenir une purification plus poussée, avec de plus faibles pertes en butadiène.The catalyst, less polluted, is more efficient, typically more selective (for the hydrogenation of acetylenic preserving at best butadiene, including because it can operate under substantially optimal operating conditions without having to compensate for the deactivation by modifying the operating conditions), and has an increased lifetime. It also allows for further purification, with lower losses of butadiene.

De façon très préférée, la fraction prélevée est soutirée à un niveau de la colonne plus élevé que le point d'alimentation de la charge. Ceci contribue à augmenter fortement le rapport C4/C5+ de la fraction prélevée.Most preferably, the withdrawn fraction is drawn off at a column level higher than the feed point of the feedstock. This contributes to greatly increase the C4 / C5 + ratio of the fraction taken.

Typiquement, le recyclage de l' effluent appauvri en composés acétyléniques issu de l'étape d'hydrogénation est réalisé à un niveau de la colonne de distillation situé au dessus du niveau de soutirage de la fraction prélevée, et au dessus des parties A et B. Par "au dessus", on entend selon l'invention que le recyclage non seulement est réalisé à un niveau plus élevé, mais également qu'il provoque un reflux interne de liquide dans les deux zones A et B (typiquement en parallèle ou en série). Ainsi, ce recyclage provoque une absorption des acétyléniques, que l'on fait refluer vers le bas de la colonne, pour obtenir un effet de concentration de ces acétyléniques dans la fraction prélevée. Corrélativement, la coupe comprenant le butadiène en tête de colonne ne contient que très peu d'acétyléniques. Le point de soutirage de cette fraction prélevée peut avantageusement se situer au point de concentration maximale des acétyléniques, en particulier du vinyl-acétylène, ou à proximité de ce point.Typically, the recycling of the effluent depleted of acetylenic compounds from the hydrogenation step is carried out at a level of the distillation column located above the withdrawal level of the fraction taken, and above the parts A and B By "above" is meant according to the invention that the recycling is not only carried out at a higher level, but also that it causes an internal liquid reflux in the two zones A and B (typically in parallel or in parallel). series). Thus, this recycling causes an absorption of acetylenic, which is refluxed down the column, to obtain a concentration effect of these acetylenic in the fraction taken. Correlatively, the cut comprising butadiene at the top of the column contains only very few acetylenics. The withdrawal point of this fraction taken can advantageously be located at the point of maximum concentration of acetylenic, in particular vinyl acetylene, or near this point.

Selon une première variante de l'invention, la partie A est constituée par un tronçon de ladite colonne situé au dessus de l'alimentation de la charge (typiquement plusieurs plateaux théoriques au dessus). Par exemple, si la colonne comprend 45 plateaux théoriques, et que l'on alimente la charge au plateau 25, on pourra soutirer une fraction prélevée au plateau 20 et la recycler après hydrogénation au plateau 10.According to a first variant of the invention, the part A is constituted by a section of said column located above the supply of the load (typically several theoretical plates above). For example, if the column comprises 45 theoretical plates, and the feed is fed to the plate 25, a fraction taken off the tray 20 can be withdrawn and recycled after hydrogenation to the plate 10.

La partie B est alors constituée par les plateaux 25 à 45. On peut alors définir une partie A distincte et non adjacente à B, qui est constituée (par exemple) par les plateaux 14 à 21. La zone de fractionnement complémentaire est typiquement constituée dans ce cas par les plateaux 1 à 21, et la zone de pré-fractionnement par les plateaux 22 à 45.Part B is then constituted by plates 25 to 45. It is then possible to define a portion A distinct and not adjacent to B, which is constituted (for example) by plates 14 to 21. The complementary fractionation zone is typically formed in this case by the trays 1 to 21, and the pre-fractionation zone by the trays 22 to 45.

Selon une deuxième variante de l'invention, la colonne de distillation comporte une partition disposée de manière à séparer la partie A de la zone de fractionnement complémentaire, de la zone B, et en ce que la zone de pré-fractionnement (4a, 4b, 6, 7) et la zone de fractionnement complémentaire (5, 6, 7) comprennent au moins une section commune (6, 7).According to a second variant of the invention, the distillation column comprises a partition arranged so as to separate the part A of the complementary fractionation zone, from zone B, and in that the pre-fractionation zone (4a, 4b , 6, 7) and the complementary fractionation zone (5, 6, 7) comprise at least one common section (6, 7).

Typiquement, la partition est disposée dans une partie centrale de la colonne, de manière à ménager une section commune (6) en tête de colonne et une section commune (7) en fond de colonne,

  • la coupe C4 comportant sensiblement tout le butadiène est récupérée dans la section commune (6) en tête de colonne,
  • la coupe enrichie en C5+ est récupérée dans la section commune (7) en fond de colonne, et
  • la fraction prélevée est produite dans ladite partie A (5) de la zone de fractionnement complémentaire, au niveau de la partie centrale de la colonne, qui est isolée de l'alimentation. Cette variante de l'invention permet d'obtenir un rapport C4/C5+ élevé pour la fraction prélevée: En effet, il sort des zones 4a et 4b du pré-fractionnement qui sont adjacentes à l'alimentation un "courant intermédiaire", précité, qui est un courant vapeur très pauvre en C5+ (en tête de la zone 4a), et un courant liquide plus riche en C5+ (en bas de 4b), ce courant étant efficacement rectifié dans la partie A (5), pour l'élimination de la majeure partie des C5+ qu'il contient. La variante de l'invention avec une partition interne permet donc d'obtenir un rapport C4/C5+ élevé pour la fraction prélevée sans augmenter sensiblement la hauteur totale de la colonne (contrairement à la variante ou la zone A est un tronçon de colonne superposé, situé plusieurs plateaux au dessus de l'alimentation. De plus, elle permet typiquement de diminuer le taux de reflux, par exemple d'environ 20%.
Typically, the partition is arranged in a central part of the column, so as to provide a common section (6) at the head of the column and a common section (7) at the bottom of the column,
  • the C4 cut comprising substantially all the butadiene is recovered in the common section (6) at the top of the column,
  • the fraction enriched in C5 + is recovered in the common section (7) at the bottom of the column, and
  • the fraction removed is produced in said part A (5) of the complementary fractionation zone, at the central portion of the column, which is isolated from the feed. This variant of the invention makes it possible to obtain a high C4 / C5 + ratio for the fraction taken off: Indeed, it leaves zones 4a and 4b of the pre-fractionation which are adjacent to the feed an "intermediate current", mentioned above, which is a very low C5 + vapor stream (at the head of zone 4a), and a liquid stream richer in C5 + (at the bottom of 4b), this current being effectively rectified in part A (5), for the elimination most of the C5 + it contains. The variant of the invention with an internal partition thus makes it possible to obtain a high C4 / C5 + ratio for the fraction taken without substantially increasing the total height of the column (contrary to the variant where zone A is a superimposed column section, In addition, it typically reduces the reflux rate, for example by about 20%.

L'étape d'hydrogénation est mise en oeuvre en présence d'hydrogène, dans un lit de catalyseur, par exemple à base de palladium/or, ou palladium/argent, ou de tout autre catalyseur d'hydrogénation sélective connu. Le choix du catalyseur n'est pas un élément essentiel de l'invention.The hydrogenation step is carried out in the presence of hydrogen, in a catalyst bed, for example based on palladium / gold, or palladium / silver, or any other known selective hydrogenation catalyst. The choice of catalyst is not an essential element of the invention.

L'invention peut également être mise en oeuvre selon plusieurs variantes additionnelles ou dispositions techniques:

  • La fraction prélevée peut notamment être récupérée par soutirage latéral dans la moitié supérieure de ladite partie A (5) de la zone de fractionnement complémentaire.
The invention can also be implemented according to several additional variants or technical provisions:
  • The fraction taken can in particular be recovered by lateral withdrawal in the upper half of said part A (5) of the complementary fractionation zone.

Selon une autre variante, le courant intermédiaire est directement envoyé sur un lit de catalyseur en présence d'hydrogène localisé dans ladite partie A de la zone de fractionnement complémentaire, au-dessous du plateau théorique supérieur de ladite partie A, par exemple dans la moitié supérieure de la partie A. Ceci permet une conception très compacte et intégrée de l'invention permettant d'éviter des transferts de fluide.According to another variant, the intermediate stream is directly sent to a catalyst bed in the presence of hydrogen located in said part A of the complementary fractionation zone, below the theoretical top plate of said part A, for example in the half This allows a very compact and integrated design of the invention to avoid fluid transfer.

Typiquement, l'effluent appauvri en composés acétyléniques est recyclé dans la section commune en tête de colonne, de préférence plusieurs plateaux théoriques (3 à 15 par exemple) au dessus des zones A et B, afin de réaliser un bon reflux des composés acétyléniques. Ceci permet d'obtenir une élimination poussée des acétyléniques.Typically, the effluent depleted of acetylenic compounds is recycled in the common section at the top of the column, preferably several theoretical plates (3 to 15 for example) above the zones A and B, in order to achieve a good reflux of the acetylenic compounds. This makes it possible to obtain a thorough elimination of acetylenics.

L'invention concerne également un dispositif pour la mise en oeuvre du procédé, et notamment un dispositif de traitement d'une charge comprenant des composés acétyléniques, du butadiène, et une fraction C5+ comprenant des composés diéthyléniques et/ou acétyléniques comprenant :

  • des moyens (1) d'alimentation de la charge,
  • des moyens de distillation (2) pourvus de moyens (24, 26) de récupération d'une coupe C4 comportant sensiblement tout le butadiène, et de moyens (31, 35) de récupération d'une coupe enrichie en C5+, les moyens de distillation permettant régalement la production d'une fraction prélevée comprenant des composés acétyléniques,
  • des moyens d'hydrogénation (12, 13) de la fraction prélevée, et
  • des moyens de recyclage (17) dans les moyens de distillation d'un effluent appauvri en composés acétyléniques provenant des moyens d'hydrogénation,
    caractérisé en ce que les moyens de distillation comportent :
  • au moins une colonne de distillation présentant une zone de pré-fractionnement, (4a, 4b, 6, 7) reliée aux moyens d'alimentation de la charge, produisant à au moins un niveau intermédiaire de la colonne au moins un courant intermédiaire comprenant des composés acétyléniques et
  • des moyens de transfert d'au moins un courant intermédiaire à teneur réduite en C5+, produit dans la zone de pré-fractionnement, vers au moins une zone de fractionnement complémentaire (5, 6, 7) dont une partie A (5) au moins est distincte et non adjacente à la partie B (4b, 7) de la zone de pré-fractionnement constituée par le plateau l'alimentation de la charge et les plateaux inférieurs, la partie A comprenant également des moyens de soutirage de la fraction prélevée à partir d'un point de A pour lequel le ratio molaire [C4 / C5+] est plus élevé que celui de la charge, ces moyens de soutirage étant reliés aux moyens d'hydrogénation.
The invention also relates to a device for carrying out the method, and in particular to a device for treating a filler comprising acetylenic compounds, butadiene, and a C5 + fraction comprising diethylenic and / or acetylenic compounds, comprising:
  • means (1) for feeding the load,
  • distillation means (2) provided with means (24, 26) for recovering a C4 cut comprising substantially all the butadiene, and means (31, 35) for recovering a C5 + enriched fraction, the distillation means also allowing the production of a withdrawn fraction comprising acetylenic compounds,
  • hydrogenation means (12, 13) of the fraction removed, and
  • recycling means (17) in the distillation means of an effluent depleted of acetylenic compounds from the hydrogenation means,
    characterized in that the distillation means comprise:
  • at least one distillation column having a pre-fractionation zone, (4a, 4b, 6, 7) connected to the feed supply means, producing at least an intermediate level of the column at least one intermediate stream comprising acetylenic compounds and
  • means for transferring at least one C5 + reduced-content intermediate stream produced in the pre-fractionation zone to at least one additional fractionation zone (5, 6, 7), at least one part A (5) of which is distinct and not adjacent to the part B (4b, 7) of the pre-fractionation zone formed by the tray feeding the feedstock and the lower trays, the part A also comprising means for withdrawing the fraction taken from from a point of A for which the molar ratio [C4 / C5 +] is higher than that of the feedstock, these withdrawal means being connected to the hydrogenation means.

Un tel dispositif, utilisé de préférence avec une mise en oeuvre selon l'une ou plusieurs des dispositions de procédé précitées (par exemple recyclage de l'effluent d'hydrogénation au dessus (et de préférence de 3 à 15 plateaux théoriques au dessus des zone A et B)), permet d'obtenir les avantages décrits pour le procédé selon l'invention.Such a device, preferably used with an implementation according to one or more of the aforementioned process arrangements (for example recycling of the hydrogenation effluent above (and preferably from 3 to 15 theoretical trays above the zones). A and B)) makes it possible to obtain the advantages described for the process according to the invention.

La colonne peut comprendre, dans certaines ou toutes les zones, du garnissage, structuré ou non, à la place des plateaux, qui constitue un équivalent technique de ces plateaux.The column may comprise, in some or all zones, packing, structured or not, instead of trays, which constitutes a technical equivalent of these trays.

Lorsque la colonne comprend une partition, cette partition peut être essentiellement constituée par une paroi, ou cloison interne. Cette paroi interne peut s'étendre le long d'un axe parallèle à l'axe longitudinal de la colonne de distillation. Cette paroi interne peut être essentiellement verticale ou inclinée avec un angle par rapport à la verticale inférieure à 45°.When the column comprises a partition, this partition may consist essentially of a wall, or internal partition. This inner wall may extend along an axis parallel to the longitudinal axis of the distillation column. This inner wall may be substantially vertical or inclined at an angle to the vertical less than 45 °.

La partition peut être également constituée par des parois internes disposées entre chaque plateau sur une section de la colonne.The partition may also consist of internal walls arranged between each plate on a section of the column.

La colonne de distillation peut comporter typiquement un nombre total de plateaux (sauf mention contraire, de plateaux théoriques, comptés depuis la tête de colonne) compris entre 20 et 50, de préférence entre 35 et 45.The distillation column may typically comprise a total number of trays (unless otherwise stated, theoretical plates, counted from the top of the column) of between 20 and 50, preferably between 35 and 45.

La zone de pré-fractionnement et la zone de fractionnement complémentaire peuvent comporter typiquement un même nombre ou un nombre différent de plateaux théoriques. La zone de pré-fractionnement ou la zone de fractionnement complémentaire peuvent généralement comporter entre 4 et 15, de préférence entre 9 et 12 plateaux théoriques qui sont séparés et non en commun.The pre-fractionation zone and the complementary fractionation zone may typically comprise the same number or a different number of theoretical plates. The pre-fractionation zone or the complementary fractionation zone may generally comprise between 4 and 15, preferably between 9 and 12 theoretical plates which are separated and not in common.

La section commune en tête de colonne peut comporter entre 1/3 et 2/3 du nombre total de plateaux théoriques. Par exemple, elle peut comporter de 10 à 30, de préférence de 12 à 25 plateaux théoriques.The common section at the head of the column can comprise between 1/3 and 2/3 of the total number of theoretical plates. For example, it may comprise from 10 to 30, preferably from 12 to 25 theoretical plates.

La section commune en fond de colonne peut, quant à elle, comporter le plus souvent de 2 à 10 plateaux théoriques.The common section at the bottom of the column may, for its part, generally comprise from 2 to 10 theoretical plates.

La charge peut être une fraction d'un effluent de vapocraquage comportant en majorité des hydrocarbures ayant entre 4 et 5 atomes de carbone, de préférence en majorité 4 atomes de carbone.The feedstock may be a fraction of a steam cracking effluent comprising, for the most part, hydrocarbons having between 4 and 5 carbon atoms, preferably predominantly 4 carbon atoms.

En particulier, la charge peut comporter au moins 50 % en poids, de préférence 70 % en poids, de manière plus préférée 90 % en poids d'hydrocarbures ayant entre 4 et 5 atomes de carbones, voire 4 atomes de carbone.In particular, the filler may comprise at least 50% by weight, preferably 70% by weight, more preferably 90% by weight of hydrocarbons having between 4 and 5 carbon atoms, or even 4 carbon atoms.

Le débit de soutirage de la fraction prélevée comprenant des acétyléniques peut être avantageusement maintenu à une valeur sensiblement égale à celle du débit d'alimentation de la charge. Par exemple, le débit de soutirage de cette fraction prélevée peut être maintenu entre 70 % et 130 % de la valeur du débit de la charge, de préférence entre 90 % et 110 % de la valeur du débit de la charge.The withdrawal rate of the collected fraction comprising acetylenics may advantageously be maintained at a value substantially equal to that of the feed rate of the feedstock. For example, the withdrawal rate of this fraction taken can be maintained between 70% and 130% of the value of the flow rate of the charge, preferably between 90% and 110% of the value of the flow rate of the charge.

Il peut être avantageux de contrôler la température du recyclage (notamment de le refroidir) afin de ne pas perturber la colonne par des variations locales de température importantes.It may be advantageous to control the temperature of the recycling (in particular to cool it) so as not to disturb the column by significant local temperature variations.

Pour une meilleure compréhension, deux modes de réalisation du procédé de l'invention sont illustrés par les figures 1 et 2. Ces modes de réalisation sont donnés à titre d'exemple et ne présentent aucun caractère limitatif. Ces illustrations du procédé de l'invention ne comportent pas l'ensemble des composantes nécessaires à sa mise en oeuvre. Seuls les éléments nécessaires à la compréhension de l'invention y sont représentés, l'homme du métier étant capable de compléter ces représentations pour mettre en oeuvre l'invention.For a better understanding, two embodiments of the method of the invention are illustrated by the figures 1 and 2 . These embodiments are given by way of example and are not limiting in nature. These illustrations of the method of the invention do not include all the components necessary for its implementation. Only the elements necessary for the understanding of the invention are represented therein, those skilled in the art being able to complete these representations to implement the invention.

Dans la Figure 1, la charge est alimentée par une conduite (1) dans une colonne de distillation (2) comportant une zone de pré-fractionnement (6, 4a, 4b, 7), une zone de fractionnement complémentaire (6, 5, 7), et une partition (3) disposée en partie centrale de manière à séparer une partie (4a, 4b) de la zone de pré-fractionnement du côté de l'alimentation de la charge, d'une partie A (5) de la zone de fractionnement complémentaire. La partition (3) est disposée dans la colonne (2) de manière à ménager une section commune (6) en tête de colonne et une section commune (7) en fond de colonne, entre les deux zones de fractionnement précitées.In the Figure 1 the feedstock is fed from a line (1) into a distillation column (2) having a pre-fractionation zone (6, 4a, 4b, 7), a complementary fractionation zone (6, 5, 7), and a partition (3) arranged in the central part so as to separate a part (4a, 4b) of the pre-fractionation zone on the feed side of the load from a part A (5) of the fractionation zone complementary. The partition (3) is arranged in the column (2) so as to provide a common section (6) at the top of the column and a common section (7) at the bottom of the column, between the two fractionation zones mentioned above.

Un courant intermédiaire à teneur réduite en C5+ (par rapport à la charge), sort sous forme vapeur du plateau supérieur de la zone 4a, et alimente la zone de fractionnement complémentaire (6, 5, 7) au niveau du plateau inférieur de la zone commune (6). Le liquide de ce plateau est réparti entre les zones (4a) et (5). Le courant vapeur issu du plateau supérieur de la zone commune (7) se répartit également, entre les zones (4b) et (5).A reduced C5 + content intermediate stream (relative to the feedstock), vaporizes out of the upper tray of zone 4a, and feeds the complementary fractionation zone (6, 5, 7) at the lower plateau of the zone. commune (6). The liquid of this plate is distributed between the zones (4a) and (5). The steam flow from the upper plateau of the common zone (7) is distributed equally between zones (4b) and (5).

Une fraction riche en composés acétyléniques, produite dans la partie A (5) de la zone de fractionnement complémentaire, est prélevée par une conduite de soutirage latéral (11) avant d'être envoyée dans un lit de catalyseur d'hydrogénation (12) à l'intérieur d'un réacteur d'hydrogénation (13). Le lit de catalyseur est un lit fixe à écoulement descendant, c'est à dire que la fraction prélevée est introduite par le haut dans le réacteur d'hydrogénation. De l'hydrogène est injecté dans le réacteur d'hydrogénation par une conduite (14). Un effluent appauvri en composés acétyléniques est récupéré par une conduite (15). Cet effluent appauvri en composés acétyléniques est refroidi dans un échangeur de chaleur (16) avant d'être recyclé dans la section commune 6 en tête de la colonne de distillation (2), par l'intermédiaire d'une conduite (17).A fraction rich in acetylenic compounds, produced in part A (5) of the complementary fractionation zone, is withdrawn by a lateral withdrawal line (11) before being sent to a bed of hydrogenation catalyst (12) to inside a hydrogenation reactor (13). The catalyst bed is a fixed bed with downward flow, that is to say that the fraction taken is introduced from above into the hydrogenation reactor. Hydrogen is injected into the hydrogenation reactor via a line (14). An effluent depleted of acetylenic compounds is recovered by a pipe (15). This depleted effluent of acetylenic compounds is cooled in a heat exchanger (16) before being recycled. in the common section 6 at the top of the distillation column (2), via a pipe (17).

En tête de la colonne (2), on récupère également, par l'intermédiaire d'une conduite (21), une coupe C4 comportant sensiblement tout le butadiène. Cette coupe est ensuite envoyée via la conduite (21) dans un condenseur (22), puis dans un séparateur (24) via une conduite (23). Une partie de cette coupe C4 est envoyée dans la colonne (2), sous forme de reflux, par une conduite (25). L'autre partie de la coupe C4 est récupérée par la conduite (26).At the top of the column (2), a cut C4 comprising substantially all the butadiene is also recovered via a pipe (21). This section is then sent via line (21) into a condenser (22) and into a separator (24) via a pipe (23). Part of this cut C4 is sent in the column (2), in the form of reflux, through a pipe (25). The other part of the C4 cut is recovered by the pipe (26).

En fond de la colonne (2), on récupère, par l'intermédiaire d'une conduite 31, une coupe C5 enrichie en oligomères. Une partie de cette coupe C5 est envoyée, par l'intermédiaire d'une conduite (32) dans un rebouilleur (33) avant d'être recyclée en fond de la colonne par une conduite (34). L'autre partie de la coupe C5 est récupérée par une conduite (35).At the bottom of the column (2), a cut C5 enriched in oligomers is recovered via a line 31. Part of this cut C5 is sent through a pipe (32) in a reboiler (33) before being recycled to the bottom of the column by a pipe (34). The other part of the C5 cut is recovered by a pipe (35).

Dans la Figure 2 on retrouve un certain nombre d'éléments de la Figure 1 décrits précédemment. On retrouve, en particulier, les éléments (1 à 7), (21 à 26) et (31 à 35) représentés à la Figure 1.In the Figure 2 we find a number of elements of the Figure 1 previously described. We find, in particular, the elements (1 to 7), (21 to 26) and (31 to 35) represented in Figure 1 .

A la différence de la Figure 1, la fraction comprenant des composés acétyléniques produite dans la partie supérieure de la partie A (5) de la zone de fractionnement complémentaire est directement envoyée dans un lit de catalyseur d'hydrogénation (51), ce lit étant localisé dans la partie A interne à la colonne, et non pas à l'intérieur d'un réacteur d'hydrogénation séparé.Unlike the Figure 1 , the fraction comprising acetylenic compounds produced in the upper portion of the portion A (5) of the complementary fractionation zone is directly sent into a bed of hydrogenation catalyst (51), this bed being located in the internal portion A to the column, and not inside a separate hydrogenation reactor.

Le lit de catalyseur est un lit fixe à écoulement descendant, c'est à dire que la fraction enrichie en composés acétyléniques est introduite par le haut du lit de catalyseur (51).The catalyst bed is a fixed downflow bed, ie the fraction enriched in acetylenic compounds is introduced through the top of the catalyst bed (51).

De l'hydrogène est injecté, par le bas, dans le lit de catalyseur d'hydrogénation (51) par l'intermédiaire d'une conduite (52). Un effluent liquide appauvri en composés acétyléniques est récupéré en dessous du lit de catalyseur (51), et une partie de cet effluent est recyclée (en utilisant une pompe non représentée) par la ligne (56) au dessus des zones (4a, 4b et 5) (par exemple 4 ou 5 plateaux théoriques au dessus), pour augmenter le reflux interne pauvre en acétyléniques, dans les parties A (5) et B (4b, 7) de la colonne.Hydrogen is injected from below into the hydrogenation catalyst bed (51) via a line (52). A liquid effluent depleted of compounds acetylenic acid is recovered below the catalyst bed (51), and a part of this effluent is recycled (using a pump not shown) by the line (56) above the zones (4a, 4b and 5) (for example 4 or 5 theoretical plates above), to increase acetylenic poor internal reflux, in the A (5) and B (4b, 7) portions of the column.

En tête de la colonne (2), on récupère, par l'intermédiaire la conduite (21), sensiblement tout le butadiène. Cette coupe est ensuite envoyée via la conduite (21) dans le condenseur (22), puis dans le séparateur (24) via la conduite (23). Le séparateur (24) est surmonté par une conduite (53) permettant la purge de l'hydrogène excédant. Une partie du butadiène est envoyée dans la colonne (2), sous forme de reflux, par une conduite (25). L'autre partie du butadiène est récupérée par la conduite (26).At the top of the column (2), is recovered through the conduit (21), substantially all the butadiene. This section is then sent via the pipe (21) into the condenser (22), then into the separator (24) via the pipe (23). The separator (24) is surmounted by a pipe (53) for purging excess hydrogen. Part of the butadiene is fed to the column (2) in the form of reflux through a pipe (25). The other part of the butadiene is recovered by the pipe (26).

Exemple 1 (selon l'art antérieur)Example 1 (according to the prior art)

Une charge C4+C5 issue d'effluents de vapocraquage, dont la composition est décrite dans le tableau 1 ci-dessous, est traitée conformément au procédé de l'art antérieur ( EP1217060A1 ). La charge est introduite dans une colonne de distillation à une température de 64°C, une pression de 0,60 MPa et un débit de 30 T/h.A C4 + C5 feedstock from steam cracking effluents, the composition of which is described in Table 1 below, is treated according to the process of the prior art ( EP1217060A1 ). The feed is introduced into a distillation column at a temperature of 64 ° C., a pressure of 0.60 MPa and a flow rate of 30 T / h.

Cette colonne comporte environ 40 plateaux théoriques (entre 50 et 120 plateaux réels selon le type de plateaux) et la charge est introduite au niveau du 20ème plateau (théorique). La colonne est maintenue à une pression de 0,50 MPa en tête et de 0,53 MPa en fond. La température dans la colonne est maintenue à 45°C en tête et à 95°C en fond.This column has about 40 theoretical plates (between 50 and 120 real trays according to the type of trays) and the load is introduced at the 20 th plateau (theoretical). The column is maintained at a pressure of 0.50 MPa at the top and 0.53 MPa at the bottom. The temperature in the column is maintained at 45 ° C overhead and 95 ° C bottom.

En tête de colonne, on récupère une coupe C4 contenant du butadiène et environ 1200 ppm de composés acétyléniques. La composition de cette coupe C4 est présentée dans le tableau 1 ci-dessous. Une partie de cette coupe est réintroduite après condensation et séparation, sous forme de reflux, en tête de colonne, tandis que l'autre partie est récupérée pour un traitement ultérieur, par exemple une extraction par solvant. Le taux de reflux, c'est à dire le rapport entre la partie de la coupe C4 réintroduite en tête de colonne et la totalité de la coupe C4 récupérée en tête de colonne, est de 2,2.At the top of the column, a C4 cut containing butadiene and approximately 1200 ppm of acetylenic compounds is recovered. The composition of this C4 cut is presented in Table 1 below. Part of this cut is reintroduced after condensation and separation, in the form of reflux, at the top of the column, while the other part is recovered for further processing, by example a solvent extraction. The reflux ratio, that is to say the ratio between the portion of the C4 cut reintroduced at the top of the column and the totality of the C4 cut recovered at the top of the column, is 2.2.

Au niveau du 23ème plateau (théorique) de la colonne, on soutire latéralement une fraction prélevée comprenant des composés acétyléniques, dont le rapport des concentrations composés acétyléniques sur le butadiène est sensiblement le plus élevé de la colonne, en l'occurrence égale à 0,025 mol/mol. Le débit de soutirage de cette fraction prélevée est égal au débit d'alimentation de la charge.At the 23 th plate (theoretical) of the column is drawn off laterally a withdrawn fraction comprising acetylenic compounds, the ratio of acetylenic compounds Merger butadiene is substantially the highest of the column, the occurrence equal to 0.025 mol / mol. The withdrawal rate of this fraction taken is equal to the feed rate of the load.

Cette fraction prélevée est introduite dans un réacteur d'hydrogénation alimenté en hydrogène dans des conditions de pression partielle qui correspondent sensiblement à la stoechiométrie de l'hydrogénation de ces composés acétyléniques. Ce réacteur contient un lit fixe de catalyseur d'hydrogénation fonctionnant en écoulement descendant, c'est à dire par introduction de la charge liquide par le haut du réacteur. Le catalyseur d'hydrogénation est à base de palladium stabilisé par de l'or sur un support d'alumine (0,2 % en poids de palladium et 0,6 % en poids d'or). Le réacteur d'hydrogénation est opéré dans les conditions suivantes :

  • Pression absolue : 0,50 MPa
  • Température : 35°C
  • Vitesse spatiale 4h-1
  • Débit d'hydrogène : 30 kg/h
This fraction taken is introduced into a hydrogenation reactor fed with hydrogen under partial pressure conditions which substantially correspond to the stoichiometry of the hydrogenation of these acetylenic compounds. This reactor contains a fixed bed of hydrogenation catalyst operating in downward flow, that is to say by introducing the liquid feed from the top of the reactor. The hydrogenation catalyst is based on palladium, stabilized with gold on an alumina support (0.2% by weight of palladium and 0.6% by weight of gold). The hydrogenation reactor is operated under the following conditions:
  • Absolute pressure: 0,50 MPa
  • Temperature: 35 ° C
  • Space velocity 4h -1
  • Hydrogen flow rate: 30 kg / h

Un effluent appauvri en composés acétylénique est recueilli, puis refroidi avant d'être recyclé dans la colonne au niveau du 6ème plateau théorique. Le refroidissement est réalisé de manière à ce que la température de cet effluent soit approximativement la même que celle du 6ème plateau théorique.An effluent depleted in acetylenic compounds is collected and then cooled before being recycled to the column at the level of the 6 th theoretical plateau. The cooling is carried out in such a way that the temperature of this effluent is approximately the same as that of the theoretical 6 th plateau.

Cet effluent appauvri en composés acétyléniques contient notamment les composés oléfiniques présents initialement dans la charge, les butadiènes qui n'ont pas été hydrogénés ainsi que les oligomères produits dans la zone d'hydrogénation. Ces composés oligomères, qui sont des produits lourds, sont recueillis en fond de colonne. Une coupe C5 comportant ces composés est prélevée en fond de colonne, dont la composition est présentée dans le tableau 1 ci-dessous. Une partie de cette coupe C5 est introduite dans un rebouilleur et recyclée en bas de colonne.This effluent depleted in acetylenic compounds contains in particular the olefinic compounds initially present in the feedstock, the butadienes which have not been hydrogenated as well as the oligomers produced in the hydrogenation zone. These oligomeric compounds, which are heavy products, are collected in the bottom of column. A C5 cut comprising these compounds is taken from the bottom of the column, the composition of which is shown in Table 1 below. Part of this C5 cut is introduced into a reboiler and recycled at the bottom of the column.

Dans cet exemple, le niveau d'alimentation de la charge dans la colonne (20ème plateau), le niveau de soutirage latéral de la fraction prélevée (23ème plateau) et le niveau de recyclage de l'effluent hydrogéné (6ème plateau) ont été choisis afin d'obtenir 1200 ppm poids d'acétyléniques dans la coupe C4 tout en minimisant la perte en 1,3-butadiène. Tableau 1 Phase Pourcentages massiques Charge liquide C4
Coupe de tête liquide C5
Coupe de fond liquide PROPANE 0,01 0,01 0,00 PROPADIENE 0,01 0,01 0,00 PROPYNE 0,02 0,03 0,00 ISOBUTANE 0,27 0,40 0,00 ISOBUTENE 13,66 20,31 0,01 1BUTENE 9,06 15,27 0,01 13BUTADIENE 32,52 46,99 0,04 NBUTANE 3,53 5,24 0,02 TRANS2BUTENE 4,26 7,06 0,06 VAC 0,73 0,05 0,01 CIS2BUTENE 2,00 3,31 0,13 1BUTYNE 0,20 0,07 0,01 12BUTADIENE 0,40 0,25 0,21 ISOPENTANE 1,67 0,11 4,87 2METHYL1BUTENE 3,21 0,15 9,46 ISOPRENE 9,52 0,34 28,28 PENTANE 3,333 0,09 9,94 TRANS2PENTEN 1,43 0,04 4,28 13CYCLOPENTADIENE 9,76 0,21 29,27 CYCLOPENTENE 0,48 0,01 1,45 1CIS3PENTADIENE 3,33 0,05 10,04 CYCLOPENTANE 0,60 0,01 1,82 15ETHYLCYCLOHEXADIENE 0,00 0,00 0,10 In this example, the feed level of the feed in the column (20 th plateau), the level of side withdrawal of the fraction taken (23 th plateau) and the recycling level of the hydrogenated effluent (6 th plateau) were chosen in order to obtain 1200 ppm by weight of acetylenic in the C4 cut while minimizing the loss of 1,3-butadiene. <u> Table 1 </ u> Phase Percentages Liquid charge C4
Liquid head cup C5
Cut of liquid bottom PROPANE 0.01 0.01 0.00 pROPADIENE 0.01 0.01 0.00 propyne 0.02 0.03 0.00 Isobutane 0.27 0.40 0.00 ISOBUTENE 13.66 20.31 0.01 1BUTENE 9.06 15.27 0.01 13BUTADIENE 32.52 46.99 0.04 NBUTANE 3.53 5.24 0.02 TRANS2BUTENE 4.26 7.06 0.06 VAC 0.73 0.05 0.01 CIS2BUTENE 2.00 3.31 0.13 1BUTYNE 0.20 0.07 0.01 12BUTADIENE 0.40 0.25 0.21 ISOPENTANE 1.67 0.11 4.87 2METHYL1BUTENE 3.21 0.15 9.46 Isoprene 9.52 0.34 28.28 PENTANE 3,333 0.09 9.94 TRANS2PENTEN 1.43 0.04 4.28 13CYCLOPENTADIENE 9.76 0.21 29.27 cyclopentene 0.48 0.01 1.45 1CIS3PENTADIENE 3.33 0.05 10.04 CYCLOPENTANE 0.60 0.01 1.82 15ETHYLCYCLOHEXADIENE 0.00 0.00 0.10

Le taux de conversion observé en composés vinyl-acétyléniques (VAC) est de 0,95 par calcul selon la relation : 1 - Masse de VAC sortie en tête de colonne / Masse de VAC entrée

Figure imgb0001
The conversion rate observed for vinyl acetylenic compounds (VAC) is 0.95 by calculation according to the relation: 1 - Mass of VAC exit at the top of the column / Mass of VAC Entrance
Figure imgb0001

Les pertes en butadiène représentent la quantité de butadiène qui n'est pas récupérée en tête de colonne, c'est à dire le butadiène qui est hydrogéné en butène au niveau du réacteur d'hydrogénation auquel s'ajoute le butadiène qui est perdu en fond de colonne dans la coupe C5. Les pertes en 1,3-butadiène, l'isomère commercialement intéressant, sont de 2,85 % en poids.Losses of butadiene represent the amount of butadiene which is not recovered at the top of the column, ie butadiene which is hydrogenated to butene at the hydrogenation reactor to which is added butadiene which is lost in the bottom column in section C5. The losses of 1,3-butadiene, the commercially interesting isomer, are 2.85% by weight.

La teneur en C5 en tête de colonne est de 1,00 % en poids.The C5 content at the top of the column is 1.00% by weight.

Exemple 2 (selon l'invention)Example 2 (according to the invention)

Une charge C4+C5 de vapocraquage ayant une composition identique à celle de l'exemple 1 est envoyée dans le dispositif de la Figure 1. Cette charge est introduite dans une colonne de distillation comportant une paroi interne, dans les mêmes conditions de pression et de température que dans l'exemple 1.A steam cracking charge C4 + C5 having a composition identical to that of Example 1 is sent into the device of the Figure 1 . This feed is introduced into a distillation column having an inner wall, under the same conditions of pressure and temperature as in Example 1.

La charge est introduite au niveau du 7ème plateau théorique de la partie centrale 4 (4a, 4b) dans laquelle se trouve la paroi interne, ce plateau étant le 20ème plateau théorique de la colonne. La partie 4 comprend 10 plateaux théoriques, la colonne comportant elle même 40 plateaux théoriques. La colonne est maintenue dans les mêmes conditions de pression et de température que dans l'exemple 1.The charge is introduced at the 7 th theoretical plateau of the central portion 4 (4a, 4b) in which the inner wall is located, this plateau being the 20 th theoretical plateau of the column. Part 4 comprises 10 theoretical plates, the column itself comprising 40 theoretical plates. The column is maintained under the same pressure and temperature conditions as in Example 1.

En tête de colonne on récupère une coupe C4 contenant du butadiène. La composition de cette coupe C4 est présentée dans le tableau 2 ci-dessous. Comme dans l'exemple 1, une partie de cette coupe est réintroduite après condensation et séparation, sous forme de reflux, en tête de colonne, tandis que l'autre partie est récupérée pour un traitement ultérieur. Le taux de reflux par rapport au distillat est de 1,7.At the top of the column is recovered a C4 cut containing butadiene. The composition of this C4 cut is presented in Table 2 below. As in Example 1, part of this cup is reintroduced after condensation and separation, in the form of reflux, at the top of the column, while the other part is recovered for further processing. The reflux ratio relative to the distillate is 1.7.

Au niveau du 3ème plateau théorique de la zone A (5) (16ème plateau théorique de la colonne), on soutire latéralement une fraction prélevée riche en composés acétyléniques, dont le rapport des concentrations composés acétyléniques sur le butadiène est égale à 0,030 mol/mol. Le débit de soutirage de cette fraction est de 30 T/h, c'est à dire égal au débit d'alimentation de la charge.At the level of the 3 rd theoretical plateau of zone A (5) (16 th theoretical plateau of the column), a collected fraction rich in acetylenic compounds is withdrawn laterally, the ratio of acetylenic compound concentrations on butadiene is equal to 0.030 mol. / mol. The withdrawal rate of this fraction is 30 T / h, that is to say equal to the feed rate of the load.

Cette fraction prélevée riche en composés acétyléniques est introduite dans un réacteur d'hydrogénation alimenté en hydrogène dans les mêmes conditions que dans l'exemple 1.This collected fraction rich in acetylenic compounds is introduced into a hydrogenation reactor fed with hydrogen under the same conditions as in Example 1.

Un effluent appauvri en composés acétyléniques est recueilli, puis refroidi avant d'être recyclé dans la colonne au niveau du 6ème plateau théorique de la section commune (6) en tête de colonne. Comme dans l'exemple 1, le refroidissement est réalisé de manière à ce que la température de cet effluent soit approximativement la même que celle de ce 6ème plateau théorique.A depleted effluent acetylenic compounds is recovered and then cooled before being recycled to the column at the 6 th theoretical plate of the common section (6) in the column heading. As in Example 1, the cooling is carried out in such a way that the temperature of this effluent is approximately the same as that of this theoretical 6 th plateau.

Une coupe C5, dont la composition est présentée dans le tableau 2 ci-dessous, est prélevée en fond de colonne. Une partie de cette coupe C5 est introduite dans un rebouilleur et recyclée en bas de colonne.A C5 cut, the composition of which is shown in Table 2 below, is taken from the bottom of the column. Part of this C5 cut is introduced into a reboiler and recycled at the bottom of the column.

Dans cet exemple, le niveau d'alimentation de la charge dans la colonne (20ème plateau théorique), le niveau de soutirage latéral de la fraction prélevée (16ème plateau théorique) et le niveau de recyclage de l'effluent hydrogéné (6ème plateau théorique) ont été choisis afin d'obtenir une perte en 1,3-butadiène de 2,85 % en poids, ce qui correspond à la perte obtenue à l'exemple 1. Tableau 2 Phase pourcentages massiques Charge liquide C4
Coupe de tête liquide C5
Coupe de fond liquide PROPANE 0,01 0,02 0,00 PROPADIENE 0,01 0,01 0,00 PROPYNE 0,02 0,03 0,00 ISOBUTANE 0,27 0,40 0,00 ISOBUTENE 13,66 20,44 0,03 1BUTENE 9,06 15,33 0,03 13BUTADIENE 32,52 47,35 0,16 NBUTANE 3,53 5,27 0,03 TRANS2BUTENE 4,26 7,07 0,08 VAC 0,73 0,05 0,02 CIS2BUTENE 2,00 3,38 0,09 1BUTYNE 0,20 0,06 0,01 12BUTADIENE 0,40 0,26 0,06 ISOPENTANE 1,67 0,11 4,80 2METHYL1BUTENE 3,21 0,08 9,48 ISOPRENE 9,52 0,09 28,40 PENTANE 3,33 0,02 9,96 TRANS2PENTEN 1,43 0,01 4,28 13CYCLOPENTADIENE 9,76 0,02 29,25 CYCLOPENTENE 0,48 0,00 1,44 1CIS3PENTADIENE 3,33 0,00 9,99 CYCLOPENTANE 0,60 0,00 1,80 15ETHYLCYCLOHEXADIENE 0,00 0,00 0,09 In this example, the feed level of the feedstock in the column (20 th theoretical plateau), the level of lateral withdrawal of the fraction taken (16 th theoretical plateau) and the level of recycling of the hydrogenated effluent (6 th theoretical plateau) were chosen in order to obtain a loss of 1,3-butadiene of 2.85% by weight, which corresponds to the loss obtained in Example 1. Table 2 Mass percentages phase Liquid charge C4
Liquid head cup C5
Cut of liquid bottom PROPANE 0.01 0.02 0.00 pROPADIENE 0.01 0.01 0.00 propyne 0.02 0.03 0.00 Isobutane 0.27 0.40 0.00 ISOBUTENE 13.66 20.44 0.03 1BUTENE 9.06 15.33 0.03 13BUTADIENE 32.52 47.35 0.16 NBUTANE 3.53 5.27 0.03 TRANS2BUTENE 4.26 7.07 0.08 VAC 0.73 0.05 0.02 CIS2BUTENE 2.00 3.38 0.09 1BUTYNE 0.20 0.06 0.01 12BUTADIENE 0.40 0.26 0.06 ISOPENTANE 1.67 0.11 4.80 2METHYL1BUTENE 3.21 0.08 9.48 Isoprene 9.52 0.09 28.40 PENTANE 3.33 0.02 9.96 TRANS2PENTEN 1.43 0.01 4.28 13CYCLOPENTADIENE 9.76 0.02 29.25 cyclopentene 0.48 0.00 1.44 1CIS3PENTADIENE 3.33 0.00 9.99 CYCLOPENTANE 0.60 0.00 1.80 15ETHYLCYCLOHEXADIENE 0.00 0.00 0.09

Le taux de conversion observé en composés vinyl-acétyléniques (VAC) est de 0,95, calculé selon la même relation présentée dans l'exemple1.The conversion rate observed for vinyl acetylenic compounds (VAC) is 0.95, calculated according to the same relationship presented in Example 1.

La teneur en composés acétyléniques en tête de colonne est de 1100 ppm pour une perte en 1,3 butadiène identique à l'exemple 1.The content of acetylenic compounds at the top of the column is 1100 ppm for a loss of 1,3 butadiene identical to Example 1.

La teneur en C5 en tête de colonne est de 0,33 % en poids.The C5 content at the top of the column is 0.33% by weight.

Le rapport C4/C5+ (C4/C5) de l'effluent prélevé est supérieur de plus de 30% à celui de l'exemple 1, indiquant une quantité notablement inférieure de pentadiène, et cyclopentadiène qui sont des précurseurs d'oligomères et polymères. Les quantités d'oligomères et de polymères et traces de C6+ éventuellement présentes dans la charges sont par ailleurs fortement réduites. La durée de vie, ainsi que la sélectivité du catalyseur d'hydrogénation sont ainsi notablement augmentées.The ratio C4 / C5 + (C4 / C5) of the effluent removed is more than 30% higher than that of Example 1, indicating a significantly lower amount of pentadiene, and cyclopentadiene which are precursors of oligomers and polymers. The amounts of oligomers and polymers and traces of C6 + possibly present in the charges are also greatly reduced. The service life, as well as the selectivity of the hydrogenation catalyst are thus significantly increased.

Exemple 3 (selon l'invention)Example 3 (according to the invention)

On reprend l'installation de l'exemple 2 mais au lieu de viser une perte en 1,3-butadiène identique à celle de l'exemple 1, on vise une teneur en composés acétyléniques en tête de colonne identique à celle obtenue dans ce même exemple 1, c'est à dire de 1200 ppm.The installation of Example 2 is repeated, but instead of aiming at a loss of 1,3-butadiene identical to that of Example 1, the aim is a content of acetylenic compounds at the head of the column identical to that obtained in this same Example 1, ie 1200 ppm.

Une charge C4+C5 de vapocraquage ayant une composition identique à celle de l'exemple 1 est envoyée dans le dispositif de la Figure 1. Cette charge est introduite dans une colonne de distillation comportant une paroi interne dans les mêmes conditions de pression et de température que dans l'exemple 2.A steam cracking charge C4 + C5 having a composition identical to that of Example 1 is sent into the device of the Figure 1 . This feed is introduced into a distillation column having an inner wall under the same conditions of pressure and temperature as in Example 2.

Comme dans l'exemple 2, la charge est introduite au niveau du 20ème plateau théorique, la colonne comportant elle même 40 plateaux théoriques. La colonne est maintenue dans les mêmes conditions de pression et de température que dans l'exemple 2.As in Example 2, the charge is introduced at the 20 th theoretical plate, the column itself having 40 theoretical plates. The column is maintained under the same pressure and temperature conditions as in Example 2.

En tête de colonne, on récupère une coupe C4 contenant du butadiène dont la composition est présentée dans le tableau 3 ci-dessous. Le taux de reflux est de 1,8.At the top of the column, a C4 cut containing butadiene is recovered, the composition of which is shown in Table 3 below. The reflux ratio is 1.8.

Au niveau du 16ème plateau, on soutire latéralement une fraction prélevée, dont le rapport des concentrations composés acétyléniques sur le butadiène est égale à 0,03 mol/mol. Comme dans l'exemple 2, le débit de soutirage de cette fraction est de 30 T/h.At the 16th tray is laterally withdrawn a fraction withdrawn, the ratio of acetylenic compounds concentrations of butadiene is equal to 0.03 mol / mol. As in Example 2, the withdrawal rate of this fraction is 30 T / h.

Cette fraction enrichie en composés acétyléniques est introduite dans un réacteur d'hydrogénation alimenté en hydrogène dans les mêmes conditions que dans les exemples 1 et 2.This fraction enriched in acetylenic compounds is introduced into a hydrogenation reactor fed with hydrogen under the same conditions as in Examples 1 and 2.

Un effluent appauvri en composés acétyléniques est recueilli, puis refroidi avant d'être recyclé dans la colonne au niveau du 6ème plateau théorique de la section commune en tête de colonne. Comme dans les exemples 1 et 2, le refroidissement est réalisé de manière à ce que la température de cet effluent soit approximativement la même que celle de ce 6ème plateau théorique.A depleted effluent acetylenic compounds is recovered and then cooled before being recycled to the column at the 6 th theoretical plate from the common section at the column head. As in Examples 1 and 2, the cooling is carried out in such a way that the temperature of this effluent is approximately the same as that of this theoretical 6 th plateau.

Une coupe C5 est prélevée en fond de colonne, dont la composition est présentée dans le tableau 3 ci-dessous. Une partie de cette coupe C5 est introduite dans un rebouilleur et recyclée en bas de colonne.A C5 cut is taken at the bottom of the column, the composition of which is shown in Table 3 below. Part of this C5 cut is introduced into a reboiler and recycled at the bottom of the column.

Les compositions en tête et en fond de colonne sont données dans le Tableau 3 ci-dessous. Tableau 3 Phase pourcentages massiques Charge liquide C4
Coupe de tête liquide C5
Coupe de fond liquide PROPANE 0,01 0,02 0,00 PROPADIENE 0,01 0,01 0,00 PROPYNE 0,02 0,03 0,00 ISOBUTANE 0,27 0,40 0,00 ISOBUTENE 13,66 20,43 0,03 1BUTENE 9,06 15,31 0,03 13BUTADIENE 32,52 47,32 0,16 NBUTANE 3,53 5,27 0,03 TRANS2BUTENE 4,26 7,07 0,08 VAC 0,73 0,05 0,02 CIS2BUTENE 2,00 3,38 0,08 1BUTYNE 0,20 0,07 0,01 12BUTADIENE 0,40 0,27 0,06 ISOPENTANE 1,67 0,13 4,77 2METHYL1BUTENE 3,21 0,09 9,46 ISOPRENE 9,52 0,10 28,40 PENTANE 3,33 0,02 9,96 TRANS2PENTEN 1,43 0,01 4,28 13CYCLOPENTADIENE 9,76 0,03 29,27 CYCLOPENTENE 0,48 0,00 1,44 1CIS3PENTADIENE 3,33 0,00 10,00 CYCLOPENTANE 0,60 0,00 1,80 15ETHYLCYCLOHEXADIENE 0,00 0,00 0,10 The compositions at the top and at the bottom of the column are given in Table 3 below. Table 3 Mass percentages phase Liquid charge C4
Liquid head cup C5
Cut of liquid bottom PROPANE 0.01 0.02 0.00 pROPADIENE 0.01 0.01 0.00 propyne 0.02 0.03 0.00 Isobutane 0.27 0.40 0.00 ISOBUTENE 13.66 20.43 0.03 1BUTENE 9.06 15,31 0.03 13BUTADIENE 32.52 47.32 0.16 NBUTANE 3.53 5.27 0.03 TRANS2BUTENE 4.26 7.07 0.08 VAC 0.73 0.05 0.02 CIS2BUTENE 2.00 3.38 0.08 1BUTYNE 0.20 0.07 0.01 12BUTADIENE 0.40 0.27 0.06 ISOPENTANE 1.67 0.13 4.77 2METHYL1BUTENE 3.21 0.09 9.46 Isoprene 9.52 0.10 28.40 PENTANE 3.33 0.02 9.96 TRANS2PENTEN 1.43 0.01 4.28 13CYCLOPENTADIENE 9.76 0.03 29.27 cyclopentene 0.48 0.00 1.44 1CIS3PENTADIENE 3.33 0.00 10.00 CYCLOPENTANE 0.60 0.00 1.80 15ETHYLCYCLOHEXADIENE 0.00 0.00 0.10

Les pertes en 1,3-butadiène sont de 2,75 %. La teneur en C5 en tête de colonne est de 0,38 % en masse. Le rapport C4/C5 est augmenté dans une proportion sensiblement identique à celle de l'exemple 2.Losses of 1,3-butadiene are 2.75%. The C5 content at the top of the column is 0.38% by weight. The C4 / C5 ratio is increased in a proportion substantially identical to that of Example 2.

Avec un réacteur d'hydrogénation fonctionnant dans les mêmes conditions de conversion que dans l'art antérieur, l'invention permet :

  • de réduire la quantité de précurseurs d'oligomères et polymères et/ou d'oligomères et polymères envoyés à l'hydrogénation, et donc d'améliorer l'activité et typiquement la sélectivité de ce catalyseur, ainsi que sa durée de vie.
  • à conversion globale constante, d'augmenter la sélectivité globale du procédé, et
  • à sélectivité globale constante, d'augmenter la conversion globale du procédé.
With a hydrogenation reactor operating under the same conversion conditions as in the prior art, the invention makes it possible:
  • to reduce the amount of oligomer and polymer precursors and / or oligomers and polymers sent to the hydrogenation, and thus to improve the activity and typically the selectivity of this catalyst, as well as its lifetime.
  • constant overall conversion, to increase the overall selectivity of the process, and
  • with constant global selectivity, to increase the overall conversion of the process.

Claims (8)

  1. A process for treating a feed comprising acetylenic compounds, butadiene and a C5+ fraction comprising diethylenic and/or acetylenic compounds, for example pentadiene and/or cyclopentadiene, in which:
    i) the feed is sent to a step for distillation carried out in a distillation column, a C4 cut that comprises substantially all of the butadiene is recovered from the head of said column, a cut that is enriched in C5+ is recovered and a drawn fraction comprising acetylenic compounds is produced;
    ii) at least a portion of said drawn fraction is treated in at least one hydrogenation step; and
    iii) an effluent that is depleted in acetylenic compounds from the hydrogenation step is recycled to the distillation step;
    characterized in that the distillation step comprises:
    • an initial step for pre-fractionation of the feed, which latter is supplied to a pre-fractionation zone (4a, 4b, 6, 7) included in a distillation column, to obtain at least one intermediate stream with a reduced C5+ content at one or more intermediate levels of the column; and
    • at least one step for fractionation by distillation of the intermediate stream or streams, carried out in a complementary fractionation zone at least a portion A (5) of which is distinct from and not adjacent to the portion B (4b, 7) of the pre-fractionation zone constituted by the feed supply plate and the lower plates, to withdraw the drawn fraction from a point in A located at a level in the column that is higher than the feed supply point and for which the mole ratio [C4/C5+] is higher than that of the feed;
    and in that recycling said effluent which is depleted in acetylenic compounds from the hydrogenation step is carried out to a level in the distillation column located above the level from which said drawn fraction is withdrawn and above said portions A and B.
  2. A process according to claim 1, in which said portion A is constituted by a section of said column located above the feed supply.
  3. A process according to claim 1, in which the distillation column comprises a partition disposed so as to separate said portion A of the complementary fractionation zone from said zone B, and in that the pre-fractionation zone (4a, 4b, 6, 7) and the complementary fractionation zone (5, 6, 7) comprise at least one common section (6, 7).
  4. A process according to claim 3, in which the partition is disposed in a central portion of the column to produce a common section (6) at the column head and a common section (7) at the column bottom,
    • the C4 cut comprising substantially all of the butadiene is recovered from the common section (6) at the column head;
    • the C5+ enriched cut is recovered from the common section (7) at the column bottom; and
    • the drawn fraction is produced in said portion A (5) of the complementary fractionation zone, at the central portion of the column.
  5. A process according to one of the preceding claims, in which said drawn fraction is recovered by withdrawal as a side stream from the upper half of said portion A (5) of the complementary fractionation zone.
  6. A process according to claim 3 or claim 4, in which said intermediate stream is sent directly to a bed of catalyst in the presence of hydrogen located in said portion A of the complementary fractionation zone below the upper theoretical plate of said portion A.
  7. A process according to one of claims 3 to 6, in which the effluent depleted in acetylenic compounds is recycled to the common section at the column head.
  8. An apparatus for treating a feed comprising acetylenic compounds, butadiene and a C5+ fraction comprising diethylenic and/or acetylenic compounds, comprising:
    • a distillation column (2) provided with means (1) for supplying feed, means (24, 26) for recovering a C4 cut comprising substantially all of the butadiene from the column head, and means (31, 35) for recovering a cut enriched in C5+, said distillation column also allowing production of a drawn fraction comprising acetylenic compounds;
    in which the distillation column comprises:
    a) a pre-fractionation zone (4a, 4b, 6, 7) connected to means for supplying feed, producing, at at least one intermediate level of the column, at least one intermediate stream comprising acetylenic compounds; and
    b) means for transferring at least one intermediate stream with a reduced C5+ content produced in the pre-fractionation zone to at least one complementary fractionation zone (5, 6, 7) at least a portion A (5) of which is distinct from and not adjacent to a portion B (4b, 7) of the pre-fractionation zone constituted by the plate supplying the feed and the lower plates, the portion A also comprising means for withdrawing said drawn fraction from a point in A at which the [C4/C5+] mole ratio is higher than that of the feed, said withdrawal means being disposed at a level that is higher than that of the feed supply means, and being connected to hydrogenation means;
    • means (12, 13) for hydrogenating the drawn fraction;
    • and means (17) for recycling an effluent which is depleted in acetylenic compounds deriving from the hydrogenation means to the distillation column, said recycle being carried out to a level in the distillation column located above the level from which said drawn fraction is withdrawn, and above said portions A and B.
EP05742728A 2004-04-09 2005-03-22 Method and device for processing a butadiene-containing feedstock Not-in-force EP1737934B1 (en)

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FR0403822A FR2868789B1 (en) 2004-04-09 2004-04-09 METHOD AND DEVICE FOR TREATING A CHARGE COMPRISING BUTADIENE
PCT/FR2005/000698 WO2005108529A1 (en) 2004-04-09 2005-03-22 Method and device for processing a butadiene-containing feedstock

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CN102381920B (en) * 2010-09-03 2013-08-14 中国石油化工股份有限公司 Method for removing alkyne in carbon 4 fraction by selective hydrogenation
US9090540B2 (en) * 2010-09-24 2015-07-28 Dow Global Technologies Llc Process for the production of methylene diphenyl diisocyanate isomer mixtures with specific isomer distributions and new products derived
US20120149957A1 (en) * 2010-12-10 2012-06-14 Uop, Llc Apparatus and process for oligomerizing one or more hydrocarbons
BR112014008703B1 (en) * 2011-11-30 2020-11-10 Dow Global Technologies Llc process for the production of a mixture of diphenyl methylene diisocyanate (mdi) isomers
WO2014055249A1 (en) * 2012-10-04 2014-04-10 Lummus Technology Inc. Butadiene extraction process
US9266795B2 (en) * 2013-03-28 2016-02-23 Uop Llc Process for the purification of 1,3-butadiene from an oxidative dehydrogenation process
WO2017100200A1 (en) * 2015-12-07 2017-06-15 Uop Llc Multi-stage selective hydrogenation process for processing of butadiene extraction unit
CN114478161A (en) * 2020-10-23 2022-05-13 中国石油化工股份有限公司 Apparatus and process for selective hydrogenation of mixed C4 stream
CN114471375B (en) * 2020-10-23 2023-02-24 中国石油化工股份有限公司 Device and method for fully hydrogenating mixed C4 material flow

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DE3302525A1 (en) * 1983-01-26 1984-07-26 Basf Ag, 6700 Ludwigshafen DISTILLATION COLUMN FOR THE DISTILLATIVE DISASSEMBLY OF AN INLET PRODUCT MULTIPLE FRACTIONS
FR2743079B1 (en) * 1995-12-27 1998-02-06 Inst Francais Du Petrole PROCESS AND DEVICE FOR SELECTIVE HYDROGENATION BY CATALYTIC DISTILLATION INCLUDING A LIQUID-GAS UPWARD CO-CURRENT REACTION ZONE
DE19838932C2 (en) * 1998-08-27 2001-02-22 Erdoelchemie Gmbh Process for the production of 1,2-butadiene
DE10022465A1 (en) * 2000-05-09 2001-11-15 Basf Ag Processing a four carbon cut from the fractionation of crude oil, useful for the recovery of 1,4-butadiene, comprises extractive distillation, selective hydrogenation and distillation
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DE10056841A1 (en) * 2000-11-16 2002-05-23 Basf Ag Distillation purification of butadiene comprises using single partitioned column
FR2818637B1 (en) * 2000-12-21 2003-02-07 Inst Francais Du Petrole PROCESS FOR THE TREATMENT OF C4 HYDROCARBONS COMPRISING BUTADIENE AND ACETYLENIC COMPOUNDS COMPRISING STAGES OF DISTILLATION AND SELECTIVE HYDROGENATION

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